A series of polyhedral oligomeric silsesquioxane (POSS) based hybrid copolymers poly(POSS-co-methyl methacrylate -co- 4-vinylbenzyl fluoroether carboxylate) (P(POSS-MMA-VBFC)) were prepared via radical polymerization and characterized by nuclear magnetic resonance, fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, gel permeation chromatography, X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy. The thermal properties of these polymers (T(d) > 250 degrees C) were improved by the introduction of POSS cage. The cotton fabrics coated with the polymers possessed excellent water and oil repellency. The water and salad oil contact angle could be achieved from 133 degrees to 159 degrees and from 127 degrees to 141 degrees respectively as the content of POSS in the polymer increased from 0 to 7.1 wt %. Moreover, the cotton fabric coated with the terpolymer was less flammable than the uncoated one. (C) 2011 Wiley Periodicals, Inc. J PolymSci PartA: Polym Chem 49: 5152-5161, 2011